Stabilization of tin-coupled polymers

ABSTRACT

The process of this invention can be utilized to stabilize tin-coupled rubbery polymers. This process involves adding a chelating diamine or a sodium alkoxide to the rubbery polymer after the tin coupling has been carried out. This invention more specifically discloses a process for improving the stability of a tin-coupled rubbery polymer which comprises adding a sodium alkoxide to the tin-coupled rubbery polymer subsequent to the time at which the tin-coupled rubbery polymer is coupled. Sodium alkoxide is a representative example of a sodium alkoxide that can be used to stabilize the tin-coupled rubbery polymer.

This is a Continuation of application Ser. No. 09/058,572, filed on Apr.10, 1998, of Wen-Liang Hsu and Adel Farhan Halasa, for STABILIZATION OFTIN-COUPLED POLYMERS, now U.S. Pat. No. 5,981,639, which is acontinuation-in-part of application Ser. No. 08/791,929, filed on Jan.31, 1997, issued as U.S. Pat. No. 5,739,182 on Apr. 14, 1998.

BACKGROUND OF THE INVENTION

Tin-coupled polymers are known to provide desirable properties, such asimproved treadwear and reduced rolling resistance, when used in tiretread rubbers. Such tin-coupled rubbery polymers are typically made bycoupling the rubbery polymer with a tin coupling agent at or near theend of the polymerization used in synthesizing the rubbery polymer. Inthe coupling process, live polymer chain ends react with the tincoupling agent thereby coupling the polymer. For instance, up to fourlive chain ends can react with tin tetrachloride thereby coupling thepolymer chains together.

The coupling efficiency of the tin coupling agent is dependant on manyfactors, such as the quantity of live chain ends available for couplingand the quantity and type of polar modifier, if any, employed in thepolymerization. For instance, tin coupling agents are generally not aseffective in the presence of polar modifiers. In any case, the actualnumber of live chain ends in the rubbery polymer is difficult toquantify. As a result, there is normally unreacted tin coupling agentleft in the polymer cement after the coupling process has beencompleted.

The free tin coupling agent is then available to react with any activeprotons present in the polymer cement to form hydrochloric acid. Forexample, excess tin coupling agent can react with most hydroxyl groupcontaining polymerization shortstops or moisture from the air. The acidgenerated can then cleave the tin-carbon bonds in the tin-coupledpolymer. Undesirable polymer degradation is, of course, the result ofthe tin-carbon bonds in the rubbery polymer being cleaved. This polymerdegradation is normally evidenced by a drop in the Mooney viscosity andmolecular weight of the polymer.

SUMMARY OF THE INVENTION

This invention relates to a process for improving the stability of atin-coupled rubbery polymer which comprises adding a tertiary chelatingamine, a sodium alkoxide, a solium alkyl sulfonate or a sodium arylsulfonate to the tin-coupled rubbery polymer subsequent to the time atwhich the tin-coupled rubbery polymer is coupled. Sodium amylate is arepresentative example of sodium alkoxide that can be utilized in theprocess of this invention.

DETAILED DESCRIPTION OF THE INVENTION

The process of this invention is applicable to virtually any type oftin-coupled rubbery polymer. Such tin-coupled rubbery polymers willtypically be synthesized by a solution polymerization techniqueutilizing an organolithium compound as the initiator.

Such polymerizations will normally be carried out in a hydrocarbonsolvent which can be one or more aromatic, paraffinic or cycloparaffiniccompounds. These solvents will normally contain from 4 to 10 carbonatoms per molecule and will be liquid under the conditions of thepolymerization. Some representative examples of suitable organicsolvents include pentane, isooctane, cyclohexane, methylcyclohexane,isohexane, n-heptane, n-octane, n-hexane, benzene, toluene, xylene,ethylbenzene, diethylbenzene, isobutylbenzene, petroleum ether,kerosene, petroleum spirits, petroleum naphtha, and the like, alone orin admixture.

In the solution polymerization, there will normally be from 5 to 30weight percent monomers in the polymerization medium. Suchpolymerization media are, of course, comprised of the organic solventand monomers. In most cases, it will be preferred for the polymerizationmedium to contain from 10 to 25 weight percent monomer. It is generallymore preferred for the polymerization medium to contain 15 to 20 weightpercent monomers.

The tin-coupled rubbery polymers stabilized in accordance with thisinvention can be made by the homopolymerization of a conjugated diolefinmonomer or by the copolymerization of a conjugated diolefin monomer witha vinyl aromatic monomer. It is, of course, also possible to makerubbery polymers which can be tin-coupled by polymerizing a mixture ofconjugated diolefin monomers with one or more ethylenically unsaturatedmonomers, such as vinyl aromatic monomers. The conjugated diolefinmonomers which can be utilized in the synthesis of rubbery polymerswhich can be tin-coupled and stabilized in accordance with thisinvention generally contain from 4 to 12 carbon atoms. Those containingfrom 4 to 8 carbon atoms are generally preferred for commercialpurposes. For similar reasons, 1,3-butadiene and isoprene are the mostcommonly utilized conjugated diolefin monomers. Some additionalconjugated diolefin monomers that can be utilized include2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene,2-phenyl-1,3-butadiene, and the like, alone or in admixture.

Some representative examples of ethylenically unsaturated monomers thatcan potentially be synthesized into rubbery polymers which can betin-coupled and stabilized in accordance with this invention includealkyl acrylates, such as methyl acrylate, ethyl acrylate, butylacrylate, methyl methacrylate and the like; vinylidene monomers havingone or more terminal CH2═CH— groups; vinyl aromatics such as styrene,α-methylstyrene, bromostyrene, chlorostyrene, fluorostyrene and thelike; α-olefins such as ethylene, propylene, 1-butene and the like;vinyl halides, such as vinylbromide, chloroethane (vinylchloride),vinylfluoride, vinyliodide, 1,2-dibromoethene, 1,1-dichloroethene(vinylidene chloride), 1,2-dichloroethene and the like; vinyl esters,such as vinyl acetate; α,β-olefinically unsaturated nitrites, such asacrylonitrile and methacrylonitrile; α,β-olefinically unsaturatedamides, such as acrylamide, N-methyl acrylamide, N,N-dimethylacrylamide,methacrylamide and the like.

Rubbery polymers which are copolymers of one or more diene monomers withone or more other ethylenically unsaturated monomers will normallycontain from about 50 weight percent to about 99 weight percentconjugated diolefin monomers and from about 1 weight percent to about 50weight percent of the other ethylenically unsaturated monomers inaddition to the conjugated diolefin monomers. For example, copolymers ofconjugated diolefin monomers with vinylaromatic monomers, such asstyrene-butadiene rubber copolymers which contain from 50 to 95 weightpercent conjugated diolefin monomers and from 5 to 50 weight percentvinylaromatic monomers, are useful in many applications.

Vinyl aromatic monomers are probably the most important group ofethylenically unsaturated monomers which are commonly incorporated intopolydienes. Such vinyl aromatic monomers are, of course, selected so asto be copolymerizable with the conjugated diolefin monomers beingutilized. Generally, any vinyl aromatic monomer which is known topolymerize with organolithium initiators can be used. Such vinylaromatic monomers typically contain from 8 to 20 carbon atoms. Usuallythe vinyl aromatic monomer will contain from 8 to 14 carbon atoms. Themost widely used vinyl aromatic monomer is styrene. Some examples ofvinyl aromatic monomers that can be utilized include styrene,1-vinylnaphthalene, 2-vinylnaphthalene, α-methylstyrene,4-phenylstyrene, 3-methylstyrene and the like.

Some representative examples of rubbery polymers which can betin-coupled and stabilized in accordance with this invention includepolybutadiene, polyisoprene, styrene-butadiene rubber (SBR),α-methylstyrene-butadiene rubber, α-methylstyrene-isoprene rubber,styrene-isoprene-butadiene rubber (SIBR), styrene-isoprene rubber (SIR),isoprene-butadiene rubber (IBR), α-methylstyrene-isoprene-butadienerubber and α-methylstyrene-styrene-isoprene-butadiene rubber.

The polymerizations employed in making the rubbery polymer are typicallyinitiated by adding an organolithium initiator to an organicpolymerization medium which contains the monomers. Such polymerizationcan be carried out utilizing batch, semi-continuous or continuoustechniques.

The organolithium initiators which can be employed in synthesizingtin-coupled rubbery polymers which can be stabilized by utilizing thetechnique of this invention include the monofunctional andmultifunctional types known for polymerizing the monomers describedherein. The multifunctional organolithium initiators can be eitherspecific organolithium compounds or can be multifunctional types whichare not necessarily specific compounds but rather represent reproduciblecompositions of regulable functionality.

The amount of organolithium initiator utilized will vary with themonomers being polymerized and with the molecular weight that is desiredfor the polymer being synthesized. However, as a general rule, from 0.01to 1 phm (parts per 100 parts by weight of monomer) of an organolithiuminitiator will be utilized. In most cases, from 0.01 to 0.1 phm of anorganolithium initiator will be utilized with it being preferred toutilize 0.025 to 0.07 phm of the organolithium initiator.

The choice of initiator can be governed by the degree of branching andthe degree of elasticity desired for the polymer, the nature of thefeedstock and the like. With regard to the feedstock employed as thesource of conjugated diene, for example, the multifunctional initiatortypes generally are preferred when a low concentration diene stream isat least a portion of the feedstock, since some components present inthe unpurified low concentration diene stream may tend to react withcarbon lithium bonds to deactivate initiator activity, thusnecessitating the presence of sufficient lithium functionality in theinitiator so as to override such effects.

The multifunctional initiators which can be used include those preparedby reacting an organomonolithium compounded with a multivinylphosphineor with a multivinylsilane, such a reaction preferably being conductedin an inert diluent such as a hydrocarbon or a mixture of a hydrocarbonand a polar organic compound. The reaction between the multivinylsilaneor multivinylphosphine and the organomonolithium compound can result ina precipitate which can be solubilized if desired, by adding asolubilizing monomer such as a conjugated diene or monovinyl aromaticcompound, after reaction of the primary components. Alternatively, thereaction can be conducted in the presence of a minor amount of thesolubilizing monomer. The relative amounts of the organomonolithiumcompound and the multivinylsilane or the multivinylphosphine preferablyshould be in the range of about 0.33 to 4 moles of organomonolithiumcompound per mole of vinyl groups present in the multivinylsilane ormultivinylphosphine employed. It should be noted that suchmultifunctional initiators are commonly used as mixtures of compoundsrather than as specific individual compounds.

Exemplary organomonolithium compounds include ethyllithium,isopropyllithium, n-butyllithium, sec-butyllithium, tert-octyllithium,n-eicosyllithium, phenyllithium, 2-naphthyllithium,4-butylphenyllithium, 4-tolyllithium, 4-phenylbutyllithium,cyclohexyllithium and the like.

Exemplary multivinylsilane compounds include tetravinylsilane,methyltrivinylsilane, diethyldivinylsilane, di-n-dodecyldivinylsilane,cyclohexyltrivinylsilane, phenyltrivinylsilane, benzyltrivinylsilane,(3-ethylcyclohexyl) (3-n-butylphenyl)divinylsilane and the like.

Exemplary multivinylphosphine compounds include trivinylphosphine,methyldivinylphosphine, dodecyldivinylphosphine, phenyldivinylphosphine,cyclooctyldivinylphosphine and the like.

Other multifunctional polymerization initiators can be prepared byutilizing an organomonolithium compound, further together with amultivinylaromatic compound and either a conjugated diene ormonovinylaromatic compound or both. These ingredients can be chargedinitially, usually in the presence of a hydrocarbon or a mixture of ahydrocarbon and a polar organic compound as a diluent. Alternatively, amultifunctional polymerization initiator can be prepared in a two-stepprocess by reacting the organomonolithium compound with a conjugateddiene or monovinyl aromatic compound additive and then adding themultivinyl aromatic compound. Any of the conjugated dienes or monovinylaromatic compounds described can be employed. The ratio of conjugateddiene or monovinyl aromatic compound additive employed preferably shouldbe in the range of about 2 to 15 moles of polymerizable compound permole of organolithium compound. The amount of multivinylaromaticcompound employed preferably should be in the range of about 0.05 to 2moles per mole of organomonolithium compound.

Exemplary multivinyl aromatic compounds include 1,2-divinylbenzene,1,3-divinylbenzene, 1,4-divinylbenzene, 1,2,4-trivinylbenzene,1,3-divinylnaphthalene, 1,8-divinylnaphthalene,1,3,5-trivinylnaphthalene, 2,4-divinylbiphenyl, 3,5,4′-trivinylbiphenyl,m-diisopropenyl benzene, p-diisopropenyl benzene,1,3-divinyl-4,5,8-tributylnaphthalene and the like. Divinyl aromatichydrocarbons containing up to 18 carbon atoms per molecule arepreferred, particularly divinylbenzene as either the ortho, meta or paraisomer and commercial divinylbenzene, which is a mixture of the threeisomers, and other compounds, such as the ethylstyrenes, also is quitesatisfactory.

Other types of multifunctional initiators can be employed such as thoseprepared by contacting a sec- or tert-organomonolithium compound with1,3-butadiene, at a ratio of about 2 to 4 moles of the organomonolithiumcompound per mole of the 1,3-butadiene, in the absence of added polarmaterial in this instance, with the contacting preferably beingconducted in an inert hydrocarbon diluent, though contacting without thediluent can be employed if desired.

Alternatively, specific organolithium compounds can be employed asinitiators, if desired, in the preparation of polymers in accordancewith the present invention. These can be represented by R(Li)x wherein Rrepresents a hydrocarbyl radical containing from 1 to 20 carbon atoms,and wherein x is an integer of 1 to 4. Exemplary organolithium compoundsare methyllithium, isopropyllithium, n-butyllithium, sec-butyllithium,tert-octyllithium, n-decyllithium, phenyllithium, 1-naphthyllithium,4-butylphenyllithium, p-tolyllithium, 4-phenylbutyllithium,cyclohexyllithium, 4-butylcyclohexyllithium, 4-cyclohexylbutyllithium,dilithiomethane, 1,4-dilithiobutane, 1,10-dilithiodecane,1,20-dilithioeicosane, 1,4-dilithiocyclohexane, 1,4-dilithio-2-butane,1,8-dilithio-3-decene, 1,2-dilithio-1,8-diphenyloctane,1,4-dilithiobenzene, 1,4-dilithionaphthalene, 9,10-dilithioanthracene,1,2-dilithio-1,2-diphenylethane, 1,3,5-trilithiopentane,1,5,15-trilithioeicosane, 1,3,5-trilithiocyclohexane,1,3,5,8-tetralithiodecane, 1,5,10,20-tetralithioeicosane,1,2,4,6-tetralithiocyclohexane, 4,4′-dilithiobiphenyl and the like.

The polymerization temperature utilized can vary over a broad range offrom about −20 C. to about 180° C. In most cases, a temperature withinthe range of about 30° C. to about 125° C. will be utilized. It istypically most preferred for the polymerization temperature to be withinthe range of about 60° C. to about 85° C. The pressure used willnormally be sufficient to maintain a substantially liquid phase underthe conditions of the polymerization reaction.

The polymerization is conducted for a length of time sufficient topermit substantially complete polymerization of monomers. In otherwords, the polymerization is normally carried out until high conversionsare attained. The polymerization is then terminated by the addition of atin coupling agent. Tin coupling agents can normally be used in order toimprove the cold flow characteristics of the rubbery polymer and rollingresistance of tires made therefrom. Tin coupling also leads to betterprocessability and other beneficial properties.

The tin coupling agent will normally be a tin tetrahalide, such as tintetrachloride, tin tetrabromide, tin tetrafluoride or tin tetraiodide.However, tin trihalides or tin dihalides can also optionally be used. Incases where tin dihalides are utilized, a linear polymer rather than abranched polymer results. To induce a higher level of branching, tintetrahalides are normally preferred. As a general rule, tintetrachloride is most preferred.

Broadly, and exemplarily, a range of about 0.01 to 4.5 milliequivalentsof tin coupling agent is employed per 100 grams of the rubbery monomer.It is normally preferred to utilize about 0.01 to about 1.5milliequivalents of the tin coupling agent per 100 grams of monomer toobtain the desired Mooney viscosity. The larger quantities tend toresult in production of polymers containing terminally reactive groupsor insufficient coupling. One equivalent of tin coupling agent perequivalent of lithium is considered an optimum amount for maximumbranching. For instance, if a tin tetrahalide is used as the couplingagent, one mole of the tin tetrahalide would be utilized per four molesof live lithium ends. In cases where a tin trihalide is used as thecoupling agent, one mole of the tin trihalide will optimally be utilizedfor every three moles of live lithium ends. The tin coupling agent canbe added in a hydrocarbon solution, e.g., in cyclohexane, to thepolymerization admixture in the reactor with suitable mixing fordistribution and reaction.

After the tin coupling has been completed, a tertiary chelating alkyl1,2-ethylene diamine, a sodium alkoxide, a sodium alkyl sulfonate or asodium aryl sulfonate is added to the polymer cement to stabilize therubbery polymer. The sodium alkoxides which can be utilized in thepractice of this invention will normally be of the formula NaOR, whereinR is an alkyl group containing from about 2 to about 24 carbon atoms.The sodium metal alkoxide will typically contain from about 4 to about20 carbon atoms. It is generally preferred for the sodium alkoxide tocontain from about 5 to about 16 carbon atoms. Sodium t-amyloxide(sodium t-pentoxide) is a representative example of a preferred sodiumalkoxide.

Sodium aryloxides can also be used to stabilize tin coupled rubberypolymers by the process of this invention. The sodium aryloxides thatcan be used are normally of the formula NaOR wherein R is an aryl groupor an alkaryl group that contains from about 6 to about 24 carbon atoms.

The sodium alkyl sulfonates that can be utilized are of the formulaNaSO₃R wherein R represents an alkyl group that contains from about 2 toabout 24 carbon atoms. The sodium aryl sulfonates that can be used areof the structural formula:

wherein R represents a hydrogen atom or an alkyl group containing from 1to about 24 carbon atoms. Sodium dodecylsulfonate is a representativeexample of such a sodium aryl sulfonate. In cases where a sodium alkylsulfonate is used it should be as pure as possible and free of acid. Ifeven a small amount of acid is present it will be necessary to furtherinclude a tertiary chelating amine, such asN,N,N′,N′-tetramethylethylenediamine (TMEDA).

The tertiary chelating amines which can be used are normally chelatingalkyl diamines of the structural formula:

wherein n represents an integer from 1 to about 6, wherein A representsan alkylene group containing from 1 to about 6 carbon atoms and whereinR¹, R², R³ and R⁴ can be the same or different and represent alkylgroups containing from 1 to about 6 carbon atoms. The alkylene group Ais the formula —(—CH₂—)_(m) wherein m is an integer from 1 to about 6.The alkylene group will typically contain from 1 to 4 carbon atoms (mwill be 1 to 4) and will preferably contain 2 carbon atoms. In mostcases, n will be an integer from 1 to about 3 with it being preferredfor n to be 1. It is preferred for R¹, R², R³ and R⁴ to represent alkylgroups which contain from 1 to 3 carbon atoms. In most cases, R¹, R², R³and R⁴ will represent methyl groups.

The tertiary chelating amines which can be employed can also be cyclictertiary chelating amines selected from the group consisting of

(1) N,N′-dialkyl piperazine which has the structural formula

(2) 1,4-diazabicyclo[2,2,2]octane which has the structural formula

(3) N,N-tetraalkyl-1,2-diaminocycloalkanes which are of the structuralformula

wherein n is an integer from 1 to 6 and wherein R¹, R², R³ and R⁴ can bethe same or different and represent alkyl groups containing from 1 toabout 6 carbon atoms,

(4) N, N′,N″,N′″-tetraalkyl-1,4,8,11-tetraazacyclododecanes which are ofthe structure formula

wherein R¹, R^(2,) R³ and R⁴ can be the same or different and representalkyl groups containing from 1 to about 6 carbon atoms and

(5) N,N′,N″-trialkyl-1,4,7-triazacyclononanes which are of thestructural formula

wherein R¹, R² and R³ can be the same or different and represent alkylgroups containing from 1 to about 6 carbon atoms.

A sufficient amount of the chelating amine should be added to complexwith any residual tin coupling agent remaining after completion of thecoupling reaction.

In most cases, from about 0.01 phr (parts by weight per 100 parts byweight of dry rubber) to about 2 phr of the chelating alkyl 1,2-ethylenediamine will be added to the polymer cement to stabilize the rubberypolymer. Typically, from about 0.05 phr to about 1 phr of the chelatingalkyl 1,2-ethylene diamine will be added. More typically, from about 0.1phr to about 0.6 phr of the chelating alkyl 1,2-ethylene diamine will beadded to the polymer cement to stabilize the rubbery polymer.

After the polymerization, tin coupling and stabilization has beencompleted, the rubbery polymer can be recovered from the organicsolvent. The rubbery polymer can be recovered from the organic solventand residue by means such as decantation, filtration, centrification andthe like. It is often desirable to precipitate the rubbery polymer fromthe organic solvent by the addition of lower alcohols containing fromabout 1 to about 4 carbon atoms to the polymer solution. Suitable loweralcohols for precipitation of the rubber from the polymer cement includemethanol, ethanol, isopropyl alcohol, normal-propyl alcohol and t-butylalcohol. The utilization of lower alcohols to precipitate the rubberypolymer from the polymer cement also “kills” any remaining livingpolymer by inactivating lithium end groups. After the rubbery polymer isrecovered from the solution, steam-stripping can be employed to reducethe level of volatile organic compounds in the rubbery polymer.

This invention is illustrated by the following examples which are merelyfor the purpose of illustration and are not to be regarded as limitingthe scope of the invention or the manner in which it can be practiced.Unless specifically indicated otherwise, parts and percentages are givenby weight.

EXAMPLE 1

In this experiment, 0.5 mmol of N,N,N′,N′-tetramethylethylenediamine(TMEDA) was added to 250 grams of tin-coupled styrene-butadiene rubber(SBR) cement having a solids content of 15 percent. The SBR cement hadbeen freshly coupled with tin tetrachloride (SnCl₄) shortly before theTMEDA was added. The fresh SBR sample had a Mooney ML-4 viscosity at100° C. of 90. Then the cement was stored at ambient temperature for 5days. The Mooney ML-4 viscosity of the SBR sample was again measured andwas determined to be 91 after having been stored for 5 days. Thus, theMooney ML-4 viscosity of the SBR sample did not change appreciablyduring the five-day period. The fact that the Mooney viscosity did notchange significantly during storage indicates that polymer degradationdid not occur during storage.

Comparative Example 2

This experiment was conducted at a control. The procedure utilized inExample 1 was repeated in this experiment except that TMEDA was notadded to the SBR cement. During the five-day storage period, the MooneyML-4 viscosity of the SBR dropped to 81. This 9-point drop in Mooneyviscosity indicates that a significant degree of polymer degradationoccurred when the TMEDA was not present in the polymer cement.

Comparative Example 3

This experiment was conducted at a comparative example where additionaltin tetrachloride was added to the polymer cement. The procedureutilized in Example 1 was repeated in this experiment except that 0.5mmol of additional tin tetrachloride was added to the SBR cement inplace of the TMEDA. During the five-day storage period, the Mooney ML-4viscosity of the SBR dropped to 28. This 62-point drop in Mooneyviscosity shows that a large amount of polymer degradation occurs when asignificant excess of tin coupling agent is present in the polymercement.

The results of Example 1 and Comparative Examples 2 and 3 are summarizedin Table I. As can be seen, the TMEDA stabilized the SBR sample (therewas no significant change in the Mooney ML-4 of the rubber). However,significant polymer degradation occurred in the controls which were notstabilized with a tertiary chelating alkyl 1,2-ethylene diamine. Thispolymer degradation is exemplified by the large drops in the Mooney ML-4viscosities of the SBR samples.

TABLE I Example Additive ML-4 ML-4 change 1 TMEDA 91 +1 2 none 81 −9 3SnCl₄ 28 −62 

EXAMPLE 4

and

Comparative Example 5

In Example 4, sodium amylate was added to a tin-coupledisoprene-butadiene rubber cement and in Comparative Example 5 sodiummethoxide was added to a second sample of the tin-coupledisoprene-butadiene rubber. The sodium amylate or sodium methoxide wasadded to the tin-coupled isoprene-butadiene at a 1:1 molar ratio to theamount of tin tetrachloride used in coupling the polymer. Thestyrene-butadiene rubber cement had been freshly coupled shortly beforethe sodium amylate or sodium methoxide was added. The isoprene-butadienerubber contained 30 percent bound isoprene and 70 percent boundbutadiene.

The rubber samples had an initial Mooney ML-4 viscosity at 100° C. ofabout 90. The tin-coupled styrene-butadiene rubber samples were aged inan oven at a temperature of 150° F. (66° C.) for a period of 21 days.The Mooney ML-4 viscosity of the rubber samples was measured afterperiods of 5 days, 8 days, 15 days and 21 days. The Mooney ML-4viscosities that were measured are after these time intervals arereported in Table II.

TABLE II Example 4 5 Additive Na amylate Na methoxide ML-4 Change @ 5days +2 +10 ML-4 Change @ 8 days +5 +17 ML-4 Change @ 15 days +8 +28ML-4 Change @ 21 days +10  +32

Variations in the present invention are possible in light of thedescription of it provided herein. While certain representativeembodiments and details have been shown for the purpose of illustratingthe subject invention, it will be apparent to those skilled in this artthat various changes and modifications can be made therein withoutdeparting from the scope of the subject invention. It is, therefore, tobe understood that changes can be made in the particular embodimentsdescribed which will be within the full intended scope of the inventionas defined by the following appended claims.

What is claimed is:
 1. A stabilized tin-coupled rubbery polymer which is made by a process which comprises adding a sodium alkoxide to the tin-coupled rubbery polymer subsequent to the time at which the tin-coupled rubbery polymer is coupled.
 2. A stabilized tin-coupled rubbery polymer as specified in claim 1 wherein the sodium alkoxide is of the formula NaOR wherein R represents an alkyl group that contains from about 2 to about 24 carbon atoms.
 3. A stabilized tin-coupled rubbery polymer as specified in claim 2 wherein from about 0.01 phr to about 2 phr of the sodium alkoxide is added to stabilize the rubbery polymer.
 4. A stabilized tin-coupled rubbery polymer as specified in claim 1 wherein the rubbery polymer is selected from the group consisting of polybutadiene rubber, polyisoprene rubber, styrene-butadiene rubber, α-methylstyrene-butadiene rubber, α-methylstyrene-isoprene rubber, styrene-isoprene-butadiene rubber, styrene-isoprene rubber, isoprene-butadiene rubber, α-methylstyrene-isoprene-butadiene rubber and α-methylstyrene-styrene-isoprene-butadiene rubber.
 5. A stabilized tin-coupled rubbery polymer as specified in claim 1 wherein the tin-coupled rubbery polymer is tin-coupled with tin tetrachloride.
 6. A stabilized tin-coupled rubbery polymer as specified in claim 4 wherein from about 0.05 phr to about 1 phr of the sodium alkoxide is added to stabilize the rubbery polymer.
 7. A stabilized tin-coupled rubbery polymer as specified in claim 6 wherein the sodium alkoxide is of the formula NaOR wherein R represents an alkyl group that contains from about 4 to about 20 carbon atoms.
 8. A stabilized tin-coupled rubbery polymer as specified in claim 7 wherein the tin-coupled rubbery polymer is tin-coupled with tin tetrachloride.
 9. A stabilized tin-coupled rubbery polymer as specified in claim 8 wherein from about 0.1 phr to about 0.6 phr of the sodium alkoxide is added to stabilize the rubbery polymer.
 10. A stabilized tin-coupled rubbery polymer as specified in claim 9 wherein the sodium alkoxide is of the formula NaOR wherein R represents an alkyl group that contains from about 5 to about 16 carbon atoms.
 11. A stabilized tin-coupled rubbery polymer as specified in claim 9 wherein the sodium alkoxide is sodium amylate.
 12. A stabilized tin-coupled rubbery polymer which is made by a process which comprises adding a sodium aryl sulfonate to the tin-coupled rubbery polymer subsequent to the time at which the tin-coupled rubbery polymer is coupled.
 13. A stabilized tin-coupled rubbery polymer as specified in claim 12 wherein the sodium aryl sulfonate is sodium dodecylbenzene sulfonate.
 14. A stabilized tin-coupled rubbery polymer as specified in claim 13 wherein from about 0.01 phr to about 2 phr of the sodium dodecylbenzene sulfonate is added to stabilize the rubbery polymer.
 15. A stabilized tin-coupled rubbery polymer as specified in claim 13 wherein from about 0.05 phr to about 1 phr of the sodium dodecylbenzene sulfonate is added to stabilize the rubbery polymer.
 16. A stabilized tin-coupled rubbery polymer as specified in claim 13 wherein from about 0.1 phr to about 0.6 phr of the sodium dodecylbenzene sulfonate is added to stabilize the rubbery polymer.
 17. A stabilized tin-coupled rubbery polymer as specified in claim 13 wherein the tin-coupled rubbery polymer is tin-coupled with tin tetrachloride.
 18. A stabilized tin-coupled rubbery polymer which is made by a process which comprises adding a sodium alkyl sulfonate to the tin-coupled rubbery polymer subsequent to the time at which the tin-coupled rubbery polymer is coupled.
 19. A stabilized tin-coupled rubbery polymer as specified in claim 18 wherein from about 0.01 phr to about 2 phr of the sodium alkyl sulfonate is added to stabilize the rubbery polymer.
 20. A stabilized tin-coupled rubbery polymer which is made by a process which comprises adding N,N′-dialkyl piperazine to the tin-coupled rubbery polymer subsequent to the time at which the tin-coupled rubbery polymer is coupled.
 21. A stabilized tin-coupled rubbery polymer as specified in claim 20 wherein about 0.01 phr to about 2 phr of the N,N′-dialkyl piperazine is added to stabilize the rubbery polymer.
 22. A stabilized tin-coupled rubbery polymer as specified in claim 20 wherein about 0.05 phr to about 1 phr of the N,N′-dialkyl piperazine is added to stabilize the rubbery polymer.
 23. A stabilized tin-coupled rubbery polymer as specified in claim 20 wherein about 0.1 phr to about 0.6 phr of the N,N′-dialkyl piperazine is added to stabilize the rubbery polymer.
 24. A stabilized tin-coupled rubbery polymer which is made by a process which comprises adding a tertiary chelating amine to the tin-coupled rubbery polymer subsequent to the time at which the tin-coupled rubbery polymer is coupled, wherein the tertiary chelating amine is of the structural formula:

wherein n is an integer from 1 to 3, wherein A represents an alkylene group containing from 1 to about 6 carbon atoms and wherein R¹, R², R³ and R⁴ can be the same or different and represent alkyl groups containing from 1 to 3 carbon atoms.
 25. A stabilized tin-coupled rubbery polymer as specified in claim 24 wherein about 0.01 phr to about 2 phr of the tertiary chelating amine is added to stabilize the rubbery polymer.
 26. A stabilized tin-coupled rubbery polymer as specified in claim 24 wherein about 0.1 phr to 0.6 phr of the tertiary chelating amine is added to stabilize the rubbery polymer.
 27. A stabilized tin-coupled rubbery polymer which is made by a process which comprises adding 1,4-diazabicyclo[2,2,2]octane to the tin-coupled rubbery polymer subsequent to the time at which the tin-coupled rubbery polymer is coupled.
 28. A stabilized tin-coupled rubbery polymer as specified in claim 27 wherein about 0.01 phr to about 2 phr of the 1,4-diazabicyclo[2,2,2]octane is added to stabilize the rubbery polymer.
 29. A stabilized tin-coupled rubbery polymer as specified in claim 27 wherein about 0.1 phr to about 0.6 phr of the 1,4-diazabicyclo[2,2,2]octane is added to stabilize the rubbery polymer.
 30. A process for improving the stability of a tin-coupled rubbery polymer which comprises adding a sodium aryl sulfonate to the tin-coupled rubbery polymer subsequent to the time at which the tin-coupled rubbery polymer is coupled, wherein the sodium aryl sulfonate is of the structural formula

wherein R represents a hydrogen atom or an alkyl group containing from 1 to about 24 carbon atoms, and wherein about 0.01 phr to about 2 phr of the sodium aryl sulfonate is added to stabilize the rubbery polymer.
 31. A process as specified in claim 1 wherein R represents an alkyl group containing from 1 to about 24 carbon atoms. 